Stabilized petroleum distillate



Patented Nov. 1 1, 1E

"Tashaaccesses IPE'LRQLEUM DKSTILLATE 30 W. Orelup, Short N. J.

/ No Drawing. Application May 31, 1193s,

- Serial rm. 211mm 8 (Ila The present invention relates to-improvementsin the art of stabilizing gasoline and other petroleum distillatesand'is a continuation in part of my copending application Serial No.613,788, filed May 26, 1932. It is well known that, generally speaking,present day commercial gasoline is unstable to light and to. prolongedstanding in the absence of light. When exposed to light or to standingfor prolonged periods, such gasolines darken in color and deposit gum.Frequently storage periods range from six months to two years.Furthermore, this instability of gasoline is a particular hindrance whenit is sought to incorporate into gasoline other substances, asforexample either for coloringpurposes or for increasing the anti-knockvalue of gasoline, since the formation of the gum-like substances ingasand the availability or tetraethyl lead and other organic metalliccompounds for other gasolines is thereby greatly increased.

My improved stabilizers may be generally described as oxides ofdinaphthyls containingone or more oxygen atoms and thus far I have foundthe following known members of this class of compounds to be of greatefiicacy:

Binaphthalene oxide oline acts to precipitate out these various addedagents. 1

The invention accordingly has for its principal object to provide arelatively stable cracked gasoline as well as a relatively stablemixture of gasoline with other ingredients such as coloring materialsand particularly anti-knock agents such as tetraethyl lead. To this endthe invention is.

concerned with the discovery of improved stabilizing agents which, whenadded to gasoline or a gasoline mixture as specified-will impart to it adesired property of stability. v

In recent years, the coloring of gasoline has assumed considerableimportance in the industry,

the object of such coloring being both to identify particular brands andalso to afiord some protection against the efiect of light. The use ormy improved stabilizers is further of value for the reason that theseagents themselves possess strong fluorescent properties which incombination with true coloring materials produce many 'distinctive coloreffects in gasoline. 'Such fluorescent propertiesare also useful when noother coloring material is present, since-they mask the objectionablenatural color of many cracked gasolines.

The'use of organic metal compounds as antiknock agents, particularlytetraethyl lead, has

now become widespread. With manygasollnes, particularly those of thecracked variety,- it is a diflicult matter tokeep the tetraethyl lead'or other metallic compound in solution, particularly when the gasolineso treated is exposed to light as occurs in the so-called visibledispensing pumps or when the treated gasoline is subjected to prolongedstanding in the absence of light. However, by the use ormy improvedstabilizers, this precipitating or decomposing tendency is arrestedincluding also the iso compound Binaphthalene dioxide 1 Binaphthaleneoxide is a good stabilizer against" light and furthermore hasfluorescent properties which are valuable in masking an undesirablecolor and also in enhancing the appearance 'of artificially coloredIuelsr. One method of preparing it is toheat beta-binaphthol to peraturewith phosphorous oiwchloride.

Iso binaphthalene oxide has stabilizing fluorescent propertiescomparablelto that of the normal compound. It may be prepared bypasspear to possess the optimum stabilizing andnuahlghtem irescentproperties. The dioxide compound is 1180 a good stabilizer but itsfluorescence is less iesirable in gasoline. It is therefore evident thatnot only is each one of these substances valuable per se but mixtures ofthemare particularly so. All three possess a blue or bluish fluorescencewith a faint yellowish color which does not interfere with their usewith other colors. Accordingly when these stabilizers are used with bluecoloring materials the amount of the latter may be substantiallyreduced. Moreover, the addition of small amounts of these substances tocolored gasoline brightens the anthraquinone coloring materials to agreat extent.

The quantity of my improved stabilizing agents to be added to thegasoline may vary considerably depending upon the nature of the gasolineand upon the effects desired, but in general I find the use of from A,to 3 pounds of the stabilizer per ten thousand gallons of gasolinesatisfactory for the purposes specified. Examples of coloring materialswith which my improved stabilizers give pleasing fluorescent effectsparticularly with binaphthalene oxide, are as follows: Di paratoluidoanthraquinone, monomethyl amido para toluido anthraquinone, l-hydroxy4-paratoluido anthraquinone. All these colors are of the anthraquinonegroup.

A specific example of a. colored stabilized gasoline is the following:

Gasoline 1 tank car or 10,000 gallons 1.4 para di-toluido anthraquinonelb. Bi-naphthalene oxide 2 lbs.

In general, an amount on the order of lb. of stabilizer per tank car issufficient for stabilizing purposes, whereas as much as two or threepounds may be useful in producing certain fluorescent effects. 7

The following series of experiments indicates the valuable nature of,these substances as stabilizers in gasoline:

The procedure followed in all of the experiments was to place a sampleof gasoline in a 4 oz. cylindrical bottle tightly closed and expose thesaid bottle to bright sunlight for a period of eight hours. Standardtrade gasoline with or without tetraethyl lead was used. In all casescontrols kept in the dark showed no apparent change over eight hours.

After exposure/as stated the following results were observed:

1. A sample of untreated gasoline was opaque and showed a deep yellowcoloration with gum deposits settled in the bottom of the bottle.

2. A sample of gasoline containing 1 lb. of binaphthalene oxide per tenthousand gallons of gasoline remained entirely clear and was notdistinguishable in appearance from the control.

3. Gasoline containing 3 cc. of tetraethyl lead fluid per gallon ofgasoline but otherwise untreated showeda heavy precipitate of leadcompound and a total loss of red color.

4. A sample containing the same amount of tetraethyl lead fluid asspecified in Example 3 and the same amount of binaphthalene oxidespecified in Example 2 showed an extremely small precipitate of the leadcompound and practically no loss of red color.

5. A sample of gasoline was treated with 1.1b. of binaphthalene dioxideper ten thousand gallons of gasoline and showed a slight yellowcoloration. Otherwise there was no change.

6. A sample of gasoline was treated with a similar amount of tetraethyllead fluid as in Example 3 and a similar amount of binaphthalene dioxideas in Example 5. After exposure a very slight precipitate was observedand a slight fading of the red colorwhich was discernible only bycomparison with the control.

In addition to stabilizing gasoline, my improved stabilizers are usefulwith other petroleum products, for example, lubricating, transformer andturbine oils' to arrest the decomposition which .normally takes placewhen these oils are used for their customary purposes. I

In addition, the presence of the above-named substance of my inventionin tetraethyl fluid itself has been found to increase the stabilitythereof. The term tetraethyl fluid is used to designate the mixture oftetraethyl lead and attendant modifying agents such as ethylenedi-bromide and monochlor-naphthalene which are customarily present. Forthis purpose, the amount of stabilizer usedmay be on the order of .01 to1%.

I claim:

1. A petroleum distillate tending to be unstable in the presence oflight containing a stabilizing agent therefor comprising a smallquantity of a compound selected from a group consisting of binaphthaleneoxide, iso binaphthalene oxide, and binaphthalene dioxide.

2. A gasoline containing an organic metallic compound as an anti-knockingredient, tending to be unstable in the presence of light, and astabilizing agent therefor comprising a small quantity of a compoundselected from a group consisting of binaphthalene oxide, isobinaphthalene oxide, and binaphthalene dioxide, said compound having theproperty of preventing precipitation of the said anti-knock ingredienton exposure to light.

3. A gasoline containing a coloring material and tending to be unstablein the presence of light and a small quantity of a stabilizing andfluorescence producing substance selected from ,the group consisting ofbinaphthalene oxide, iso binaphthalene oxide, and binaphthalene dioxide.4. A petroleum distillate tending to be unstable in the presence oflight, and containing a small quantity of binaphthalene oxide as astabilizer.

5. A petroleum distillate tending to be unstable in the presence oflight, and containing a small quantity of iso binaphthalene oxide as astabilizer. 6. A petroleum distillate tending to be unstable in thepresence of light, and containing a small quantity of binaphthalenedioxide as a stabilizer. '7. The method of stabilizing gasoline againstthe effect of lightwhich consists in adding thereto a small quantity ofa compound selected from the group consisting of binaphthalene oxide,iso binaphthalene oxide, and binaphthalene dioxide. 8. A gasolinecontaining tetraethyl fluid and a small quantity of a compound selectedfrom the group consisting of binaphthalene oxide, iso binaphthaleneoxide and binaphthalene dioxide.

JOHN W. ORELUP.

CERTIFICATE OF CORRECTION.

Patent No. 2,262,LL66. November 11, l9l l.

JOHN W. ORELUP.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,second colnmn, line 26, for the word "to' before "1 read -of--; and thatthe said Letters Patent should be read with this correction therein thatthe same may conform to the record of the case in the Patent Office.

Signed and sealed this 15th day of January, A. D. 19L 2.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents CERTIFICATE OF CORRECTION. PatentNo. 2,262A66. November 11, 19M.

JOHN w. ORELUP.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,second column, line 26, for the word "to" before "1%" read -of-; andthat the said Letters Patent should be read with this correction thereinthat the same may conform to the record of the case in the PatentOffice.

sign d and sealed this 15th day of January, A. D. 19L 2.

. Henry Van Arsdale, (Seal) Acting Commissioner of Patents

